Collision‐Induced E(0g+)−D(0u+) State‐to‐State Energy Transfer in I₂

Abstract

Electronic energy transfer in the E(0g+) D(0+) system of I2 is investigated in an experiment, where single rovibrational quantum states are prepared, single collision conditions prevail, and the final states have been determined from dispersed fluorescence. In I (E) X (X Ar, N2, 02) the collisional decay is found to be governed by minimum energy transfer. With (X I2) an anomalous behaviour is found for the initially prepared E, v 8, J 56 level, which is tentatively ascribed to vibrational excitation of the collision partner. Keywords." Energy transfer; iodine; ion-pair state; fluorescence B3YI(0+) electronic state of iodine and bromine is often used as a prototype system [1]. Collisional relaxation data were put in a semi-empirical perspective by several authors [2, 3]. In most experimental studies

The influence of amplified spontaneous emission in collisional energy transfer studies exemplified by to transfer in I2

“…The spectra shown in the upper and lower traces in Fig. 4 reproduce those reported by Ubachs et al [5,6] and Bibinov et al [4], respectively, and which were displayed in Fig. 4 of Ref.…”

“…There were less marked differences between the two earlier data sets for (v = 9, 13 and 15) of the E0 þ g ð 3 P 2 Þ state [4,6]. However, for all three levels there was an enhancement of the transfer with the largest FCF in the study where ASE transfer was observed from (v = 8) [6].…”

“…Simulations of the spectra showed that the upper trace emission came from (v = 10, 11 and 12) in the ratio 1.0:0.24:0.24 [6], while the lower came from a distribution of the same three levels in which (v = 11) was most highly populated [4]. Previously, both spectra had been attributed to collisional transfer from the initially excited E0 þ g ð 3 P 2 Þ state [4][5][6] but the discrepancy between the two could not be explained [4]. Our results show that in one of the previous studies [4] the transfer really was collision-induced but in the other two [5,6] it was predominantly ASE-induced.…”

“…In the case of transfer from (v = 0) of the E0 þ g ð 3 P 2 Þ state, it was shown that the vibrational level distribution in the D0 þ u ð 3 P 2 Þ state was determined by a combination of the energy mismatch and the FCFs [2]. In contrast, transfer from (v = 8-55) of the E0 þ g ð 3 P 2 Þ state was reported to be determined almost uniquely by the energy mismatch effect with practically no correlation with the FCFs [3][4][5][6]. An anomalous result for (v = 8) in which the transfer was dominated by FCFs was observed by one group [5,6] but could not be subsequently reproduced by a second group [3,4].…”

Non-adiabatic , D′, β, γ, δ transitions in the first ion-pair tier of molecular iodine induced by collisions with I2, N2 and CO2

“…M other IP statesÞ non-adiabatic transitions induced by collisions with molecular partners different from the I 2 (X) is very scarce. Data on kinetics of the transitions from the E state to the D one induced by collisions with N 2 and CF 4 are only available in the literature [7,[12][13][14]. Besides, very recently, Hutchison et al studied I 2 ðE !…”